44 The Laws of Thermodynamics 44-1 Heat engines; the first law So far we have been discussing the properties of matter from the atomic point of view, trying to understand roughly what will happen if we suppose that things are made of atoms obeying certain laws. However, there are a number of relation- ships among the properties of substances which can be worked out without con- sideration of the detailed structure of the materials. The determination of the relationships among the various properties of materials, without knowing their internal structure, is the subject of thermodynamics. Historically, thermodynamics was developed before an understanding of the internal structure of matter was achieved, To give an example: we know from the kinetic theory that the pressure of a gas is caused by molecular bombardment, and we know that if we heat a gas, so that the bombardment increases, the pressure must increase, Conversely, if the in a container of the gas is moved inward against the force of bombardment, the energy of the molecules bombarding the piston will increase, and consequently the temperature will increase. So, on the one hand, if we increase the temperature at a given volume, we increase the pressure. On the other hand, if we compress the gas, we will find that the temperature will rise. From the kinetic theory, one can derive a quantitative relationship between these two effects, but instinctively ‘one might guess that they are related in some necessary fashion which is independ ent of the details of the collisions. Let us consider another example, Many people are familiar with this interest- ing property of rubber: If we take a rubber band and pull it, it gets warm. If one puts it between his lips, for example, and pulls it out, he can feel a distinct warming, and this warming is reversible in the sense that if he relaxes the rubber band quickly while it is between his lips, itis distinctly cooled. That means that when we stretch a rubber band it heats, and when we release the tension of the band ts might suggest that if we heated a band, it might pull: that the fact that pulling a band heats it might imply that heating a band should cause it to contract. And, in fact, if we apply a gas lame to a rubber band holding a weight, we will see that the band contracts abruptly (Fig. 44-1). So itis true that ‘when we heat a rubber band it pulls, and this fact is definitely related to the fact that when we release the tension of it, it cools. The internal machinery of rubber that causes these effects is quite complicated. We will describe it from a molecular point of view to some extent, although our ‘main purpose in this chapter is to understand the relationship of these effects independently of the molecular model. Nevertheless, we can show from the molec- ular model that the effects are closely related, One way to understand the behavior of rubber is to recognize that this substance consists of an enormous tangle of long chains of molecules, a kind of “molecular spaghetti,” with one extra compli- cation: between the chains there are cross-links—like spaghetti that is sometimes welded together where it crosses another piece of spaghetti—a grand tangle, When we pull out such a tangle, some of the chains tend to line up along the direc- tion of the pull. At the same time, the chains are in thermal motion, so they hit each other continually. It follows that such a chain, if stretched, would not by itself remain stretched, because it would be hit from the sides by the other chains and other molecules, and would tend to kink up again, So the real reason why a rubber band tends to contract is this: when one pulls it out, the chains are length- wise, and the thermal agitations of the molecules on the sides of the che 44.1 Heat engines; the first law 44.2 The second law 44.3 Reversible engines 4-4 The efficiency ofan ideal ‘engine 44.5 The thermodynamic temperature 44-6 Entropy Fig. 44-1. The heated rubber band.Fig. 44-2. eng ‘The rubber-band heat to kink the chains up, and make them shorten. One can then appreciate that ifthe chains are held stretched and the temperature is increased, so that the vigor of the bombardment on the sides of the chains is also increased, the chains tend to pull in, and they are able to pull a stronger weight when heated. If, after being stretched for a time, a rubber band is allowed to relax, each chain becomes soft, and the molecules striking it lose energy as they pound into the relaxing chain, So the temperature fas We have seen how these two process, contraction when heated and cooling uring relaxation, can be related by the kinetic theory, but it would be a tremendous challenge to determine from the theory the precise relationship between the two. ‘We would have to know how many collisions there were each second and what the chains look like, and we would have to take account of all kinds of other complica- tions. The detailed mechanism is so complex that we cannot, by kinetic theory, really determine exactly what happens; still, a definite relation between the two cffects we observe can be worked out without knowing anything about the internal ‘machinery! ‘The whole subject of thermodynamics depends essentially upon the following kind of consideration: because a rubber band is “stronger” at higher temperatures than itis at lower temperatures, it ought 10 be possible to lift weights, and to move them around, and thus to do work with heat, In fact, we have already seen experimentally that a heated rubber band can lift a weight. The study of the way that one does work with heat is the beginning of the science of thermodynamics Can we make an engine which uses the heating effect on a rubber band to do work? One can make a silly looking engine that does just this. It consists of a bicycle wheel in which all the spokes are rubber bands (Fig. 44-2). If one heats the rubber bbands on one side of the wheel with a pair of heat lamps, they become “stronger” than the rubber bands on the other side. ‘The center of gravity of the wheel will be pulled to one side, away from the bearing, so that the wheel turns, As it turns, cool rubber bands move toward the heat, and the heated bands move away from the heat and cool, so that the wheel turns slowly so long as the heat is applied. The efficiency of this engine is extremely low. Four hundred watts of power pour into the two lamps, but it is just possible to lift ly with such an engine! An inter- esting question, however, is whether we can get heat to do the work in more efficient ways. In fact, the science of thermodynamics began with an analysis, by the great engineer Sadi Carnot, of the problem of how to build the best and most efficient engine, and this constitutes one of the few famous cases in which engincering has contributed fundamentally to physical theory. Another example that comes to mind is the mote recent analysis of information theory by Claude Shannon. ‘These two analyses, incidentally, turn out to be closely related, Now the way a steam engine ordinarily operates is that heat from a fire boils, some water, and the steam s0 formed expands and pushes on a piston which makes a wheel go around. So the steam pushes the piston—what then? One has to finish the job: a stupid way to complete the cycle would be to let the steam escape into the air, for then one has to keep supplying water. It is cheaper—more effcient— to let the steam go into another box, where itis condensed by cool water, and then pump the water back into the boiler, so that it circulates continuously. Heat is thus supplied to the engine and converted into work. Now would it be better to Use alcohol? What property should a substance have so that it makes the best possible engine? That was the question to which Carnot addressed himself, and one of the by-products was the discovery of the type of relationship that we have just explained above. The results of thermodynamics are all contained implicitly in certain app cntly simple statements called the laws of thermodynamics. At the time when Carnot lived, the first law of thermodynamics, the conservation of energy, Was not known. Carnot’s arguments were so carefully drawn, however, that they are valid even though the first law was not known in his time! Some time afterwards, Clausius made a simpler derivation that could be understood more easily than Carnot’s very subtle reasoning. But it turned out that Clausius assumed, not the conserva- 42tion of energy in general, but that heat was conserved according to the calorie theory, which was later shown to be false. So it has often been said that Carnot’s logic was wrong. But his logic was quite correct. Only Clausius’ simplified ver- sion, that everybody read, was incorrect. ‘The so-called second law of thermodynamics was thus discovered by Carnot before the first law! It would be interesting to give Carnot’s argument that did not use the first law, but we shall not do so because we want to learn physics, not history. We shall use the first law from the start, in spite of the fact that a great deal can be done without it. Let us begin by stating the first law, the conservation of energy: if one has a system and puts heat into it, and does work on it, then its energy is increased by the heat put in and the work done. We can write this as follows: The heat Q put into the system, plus the work W done on the system, is the increase in the energy U of the system; the latter energy is sometimes called the internal energy: Change in U = @ + W. 4.) The change in U can be represented as adding a little heat AQ and adding a little work AW: aU = a0 +m, (44.2) which is a differential form of the same law. We know that very well, from an earlier chapter. 44-2 The second law ‘Now, what about the second law of thermodynamics? We know that if we do work against friction, say, the work lost fo us is equal to the heat produced If we do work in a room at temperature T, and we do the work slowly enough, the room temperature does not change much, and we have converted work into heat ata given temperature. What about the reverse possibility? Isit possible to convert the heat back into work at a given temperature? The second law of thermo- <éynamies asserts that it is not. It would be very convenient to be able to convert heat into work merely by reversing a process like friction. If we consider only the conservation of energy, we might think that heat energy, such as that in the vibra tional motions of molecules, might provide a goodly supply of useful energy. But Carnot assumed that it is impossible to extract the energy of heat at a single temperature. In other words, if the whole world were at the same temperature, ‘one could not convert any ofits heat energy into work: while the process of making work go into heat can take place at a given temperature, one cannot reverse it 10 get the work back again. Specifically, Carnot assumed that heat cannot be taken in at a certain temperature and converted into work with no other change in the system or the surroundings. That last phrase is very important. Suppose we have a can of compressed air at a certain temperature, and we it the air expand, It can do work; it can make hammers go, for example. It cools off a litle in the expansion, but if we had a big sea, like the ovean, at a given temperature—a heat reservoir—we could warm it up again. So we have taken the heat out ofthe sea, and we have done work with the compressed air. But Carnot was not wrong, because we didnot leave everything as it was. If we recompress the air that we let expand, we will ind we are doing extra work, and when we are finished we will discover that we not only got no ‘work out of the system at temperature 7, but we actually put some in, We must talk only about situations in which the ne result ofthe whole process i to take heat away and convert it into work, just as the net result of the process of doing work against friction is to take work and convert it into heat. If we move in a circle, we can bring the system back precisely to its starting point, with the net result that we did work against frievion and produced heat. Can we reverse the process? Turn a switch, so that everything goes backwards, so the friction does work against us, and cools the sea? According to Carnot: no! So let us suppose that this is impossible 43